Process for removing acid components from hydrocarbon solutions



Patentedv Mar. 7, 1939 PATENT 'o'FFic PROCESS FOR REMOVING ACID COMPO- NEN TS FROM HYDROCARBON SOLUTIONS David Louis Yabrolf, Berkeley, and Ellis R. White, Albany, Calii'., assignors to Shell Development Company, San Francisco, Calif., a corporation or Delaware No Drawing. Application January 2, 1937, .Serial No. 118.920

'7 Claims.

This invention relates to the removal of weakly acid-reacting organic substances from solutions in organic liquids of'the type of hydrocarbons, and in particular deals with the removal of mercaptans from petroleum distillates.

It' is frequently necessary to eliminate small quantities of organic acidic components such as mercaptans and phenols, etc. from their solutions in substantially neutral hydrocarbon type liquids. The term, hydrocarbon type liquids, as herein used, refers to hydrophobe normally liquid organic substances which are neutral or slightly basic, such as the liquid hydrocarbons derived from petroleum, benzene, toluene, xylene, substituted normally liquid hydrocarbons which are substantially insoluble in water, for instance, chlorinated hydrocarbons, of which chlorethane, ethylene dichloride, trichlorethylene, carbon tetrachloride, chlorpropane, chlorbutylene, chlorbenzene, brombenzene, are examples; or nitro hydrocarbons, for example, nitroethane, nitrobenzene; or other nitrogen containing hydrocarbons such as amyl or higher amines, aniline, pyridine, petroleum bases, etc.

In the U. S. Patent 2,059,075 by Yabrofi and Givens it was shown that the efficacy of the removal of acidic organic substances from their solution in hydrocarbon type liquids by means of alkaline-reacting solutions which are substantially immiscible with said liquids, depends largely on the solvent power of the alkaline solution for the organic acids and on the alkalinity of the former. As a means for producing aqueous alkaline solutions of good solvent power for organic 35 acids the use of quaternaryammonium bases was suggested. The addition of certain polyhydroxy alcohols, amino alcohols, and diamines to aqueous alkali hydroxide to increase the solvent power of the latter was disclosed in the pending applications Serial Nos. 102,892 and 102,893, filed Sep tember 28, 1936, by Yabrofl'.

Now we have discovered that the alkali salts of certain lower fatty acids have'the ability of increasing the extraction power of aqueous alkali toward organic acidsto a remarkable degree by virtue of the combination of two properties, namely high solubility in aqueous caustic alkali and high solubility enhancing effect.

The terms alkali, alkali hydroxide, or caustic alkali refer to all strongly alkaline bases, 1. e., the alkali metal and ammonium hydroxides, alkaline earth hydroxides, quaternary ammonium bases, alkaline reacting carbonates and bicarbonates, etc., although the hydroxides of the alkali metals are preferred. Especially useful are the sodium and potassium hydroxides, as being the strongest of the easily available bases. While sodium hydroxide is more generally used because of its lower cost, potassium hydroxide is usually considered more effective.

The salts which are used according to this invention are the alkali salts of the acids having from 3 to 5 carbon atoms, the most outstanding salt being the isobutyrate.

Solubility enhancing efi'ect increases with the concentration of the solubility promoter salt as well as with the strength 01' the caustic alkali. In the table below this eflect is demonstrated. A solution of normal amyi mercaptan in iso-octane was treated in a single stage with various aqueous sodium hydroxide solutions containing different amounts of sodium isobutyrate, and the tabulated data represent the partition coefficients K for n-amyl mercaptan between the aqueous sodium hydroxide and iso-octane, K being the concentration of the mercaptan dissolved as a mercaptide in the aqueous caustic phase divided by its concentration in the hydrocarbon phase.

' TABLE I K values for n-amyl mercaptan in isooctane and various concentrations of NaOH Grams Na-isobutyrate in milliliters in 2.0 N NaOH 3.5 N NaOH 5.0 N NaOiI caustic From the above data the importance of high solubility of the fatty acid salt in strong aqueous caustic is realized, since highest extraction efliciency' can be obtained only by the combination of high alkalinity and high fatty acid salt content.

The solubilities of some typical fatty acid salts in 5 N -aqueous sodium hydroxide are as follows:

TABLE II solubilities of salts in 5 N-caustic soda Potassium salts, being somewhat more soluble in aqueous caustic alkali, are in general capable of giving better extraction results. The greater solubilities of the potassum salts is particularly marked in sodium hydroxide solutions rather TABLE III Eflect of the acid radical size on K values K values for n-nmyl Number of C atoms in fatty said salt morcaniun The maximum K values which can be reached with any one fatty acid salt depend upon the optimum combination of its solubility and concentration of the alkali hydroxide. Fatty acid salts of less than 3 carbon atoms having low solubility enhancing effects, have'relatively'low maximum K values which compare unfavorably with other solutizers which have been disclosed in other applications; and fatty acid salts of more than carbon atoms, although possessing favorable solubility enhancing properties, are insufficiently soluble in aqueous caustic alkali to exercise a solubility enhancing effect of practical value. Moreover, fatty acid salts of about and more carbon atoms are likely to produce stubborn emulsions, a difficulty which is not encountered when using lower fatty acids.

Maximum K values for n-amyl mercaptan between iso-octane and 5 N sodium hydroxide saturated with alkali metal salts of the various fatty acids, are shown in Table IV below.

TABLE IV Maximum K values for n-amul mercaptan and different solubility promoters Number of g ng}? K for Suit 0 atoms 5 N NaOH n-amyl in salt grams [100 cc. mercaptan 0 1.0 2 1. 8 3 15. b 4 28 16 4 46 140 4 210 5 l4 8 5 12 8. ii Na-ncuproate 6 0. 7 4. 5

In one particular case, a California gasoline distillate boiling from 150" to 200 C. containing 076% mercaptan sulfur was extracted with 20% by volume of a 5 normal sodium hydroxide solution containing 40 grams sodium isobutyrate per 100 milliliters of solution in a 3-stage countercurrent extractor. The mercaptan sulfur was reduced to .001%, while an aqueous caustic alkali solution containing no isobutyrate'reduced the tracting power.

mercaptan content under similar conditions to .03% only.

Although the solubilities of the fatty acid salts increase with increasing temperatures, the application of elevated temperatures for extraction offers few advantages, if any, because the extraction power of solutized caustic for weak acids, such as mercaptans, decreases with increasing temperatures. crate at temperatures between about 0 to C.

While in comparison with some of the solutizing agents disclosed in the earlier applications hereinbefore referred to, the fatty acid salts are slightly inferior as far as their solutizing powers are concerned, they have the great advantage of be ing fully insoluble in hydrocarbon type liquids in contrast to the polyhydroxy alcohols, amino alcohols, and diamines, which are slightly soluble therein. Thus, losses of the fatty acid salts from this source are non-existing.

Moreover, the salts are not volatile, which facilitates the recovery of the spent caustic by steaming, since no losses of the fatty acid salt by vaporization can occur. Steaming can be carried out simply by blowing steam through the spent caustic alkali containing solubility promoter solution, which may be maintained as a pool or by flowing it downward through a suitable tower in countcr current to the ascending steam, or in any other suitable manner. The used steam, which after passage through the spent caustic alkali solution carries with it mercaptans, need not be carefully fractionated as in the case of volatile solubility promoters, since it contains no solubiiity promoter.

The removal of mercaptans from the spent caustic alkali for the purpose of regenerating same must be carried as far as is economically feasible, because a retention of mercaptans in the regenerated caustic alkali greatly lessens its ex- For instance, upon extracting the afore mentioned California gasoline distillate which contains 076% mercaptan sulfur, with 10% by volume of a 5-normal sodium hydroxide solution containing 40 grams isobutyrate per 10 milliliters solution and various amounts of mercaptides, in a 3-stage countercurrent extractor, the

Therefore, I usually prefer to op-' mercaptan sulfur of the distillate was reduced as follows:

TABLE V Efiect of mercaptides in the caustic alkali contaming solubility promoter on mercaptan removal Moron )tan sul- Initisl morcaptlde suliurincsustic, g g l g' l mom/mt traction 0 0. 002 .05 .008 10 Oil 20 010 captans and stronger acids in a'suitable manner to remove the stronger acids, as by washing with water to remove acetic acid and the like, scrubbing it with a. caustic alkali free from solubility prosubjecting the pretreated liquid to the treatmenth'ereinbefore described.

We claim as our invention:

1. In the process of separating organic acidreacting substances contained in a water-insoluble' neutral or basic; organic liquid the steps comprising treating said liquid with an aqueous solu tion of a strong alkaline base containing a substantial amount of dissolved salt of a fatty acid having from 3 to carbon atoms under conditions to absorb at least a portion of said acid-reacting substances in said aqueous solution and to form two liquid layers, one comprising the aqueous solution containing absorbed acid-reacting substances and the other. consisting essentially-of the treated organic liquid, and separating the 4. The process of claim 1 in which the aqueous caustic is substantially saturated'with the fatty acid salt.

5. In the process of separating mercaptans from sour hydrocarbon oil by treating same with an aqueous alkali metal hydroxide solution, the improvement comprising subjecting said oil to a treatment with an aqueous solution of alkali metal hydroxide which is substantially saturated with a fatty acid salt having from 3 to 5 carbon atoms, under conditions to absorb at least a portion of said mercaptans in the alkali metal hydroxide solution thereby forming mercaptides, and to form two layers, one comprising the aqueous solution of alkali metal hydroxide containing fatty acid salt and mercaptides and the other consisting essentially of treated hydrocarbon oil, and separating the layers.

6. In the process of separating mercaptans from a sour hydrocarbon oil by treating same with an aqueous alkali metal hydroxide solution, the improvement comprising subjecting said oil to a treatment with an aqueous solution of sodium hydroxide which contains about 40 grams sodium isobutyrate per 100 milliliters solution under conditions to absorb at least a portion of the mercaptans in the sodium hydroxide solution, thereby forming mercaptides, and to form two layers, one comprising the aqueous sodium hydroxide solution containing the isobutyrate and mercaptides 1 and the other consisting essentially of treated oil, 

